Principles of melting in hybrid organic–inorganic perovskite and polymorphic ABX3 structures. Issue 7 (1st February 2022)

• Record Type: Journal Article
• Authors: Shaw, Bikash Kumar; Castillo-Blas, Celia; Thorne, Michael F.; Ríos Gómez, María Laura; Forrest, Tom; Lopez, Maria Diaz; Chater, Philip A.; McHugh, Lauren N.; Keen, David A.; Bennett, Thomas D.
• Is Part Of: Chemical science. Volume 13:Issue 7(2022)
• Page Start: 2033
• Page End: 2042
• Publication Date: 2022-02-01
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d1sc07080k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Increasing the size of the A-site cation from (C3 H7 )4 N → (C4 H9 )4 N → (C5 H11 )4 N in hybrid organic–inorganic ABX3 structures was observed to result in a decrease in T m, through an increase in Δ S f . Abstract : Four novel dicyanamide-containing hybrid organic–inorganic ABX3 structures are reported, and the thermal behaviour of a series of nine perovskite and non-perovskite [AB(N(CN)2 )3 ] (A = (C3 H7 )4 N, (C4 H9 )4 N, (C5 H11 )4 N; B = Co, Fe, Mn) is analyzed. Structure–property relationships are investigated by varying both A-site organic and B-site transition metal cations. In particular, increasing the size of the A-site cation from (C3 H7 )4 N → (C4 H9 )4 N → (C5 H11 )4 N was observed to result in a decrease in T m through an increase in Δ S f . Consistent trends in T m with metal replacement are observed with each A-site cation, with Co < Fe < Mn. The majority of the melts formed were found to recrystallise partially upon cooling, though glasses could be formed through a small degree of organic linker decomposition. Total scattering methods are used to provide a greater understanding of the melting mechanism.